CN117117328B - Electrolyte and lithium ion battery containing same - Google Patents

Electrolyte and lithium ion battery containing same Download PDF

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CN117117328B
CN117117328B CN202311371375.4A CN202311371375A CN117117328B CN 117117328 B CN117117328 B CN 117117328B CN 202311371375 A CN202311371375 A CN 202311371375A CN 117117328 B CN117117328 B CN 117117328B
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electrolyte
reacting
temperature
dihydro
molar ratio
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CN117117328A (en
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黄文达
刘建生
蒋灵
王良虎
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Shenzhen Huachi New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an electrolyte and a lithium ion battery containing the electrolyte, wherein the electrolyte is prepared by adding 8-10% of strengthening additive by mass percent into the electrolyte of PC/DEC (polycarbonate/digital electron acceptor) of 1.0M lithium hexafluorophosphate, the electrolyte can form a reticular molecular chain, so that the thermodynamic property of an SEI (solid electrolyte interface) film is better, solvent molecules are prevented from directly contacting with an electrode, the co-insertion of the solvent molecules to the electrode is avoided, the cycle performance and the service life of the battery are further improved, the main chain of the additive contains a biphenyl structure which can play the role of overcharge protection, meanwhile, the chain reaction of hydroxyl radicals can be prevented by the organic phosphorus-sulfur structure, the safety performance of lithium ions can not be improved due to the combustion of the organic electrolyte, the sulfur element has strong electronegativity, the electron absorption capability of the SEI film is stronger, the charge-discharge efficiency of the battery is improved, the side chain contains a siloxane structure which can increase the adsorptivity with an electrode material, and the stability of the SEI film is improved.

Description

Electrolyte and lithium ion battery containing same
Technical Field
The invention relates to the technical field of lithium battery preparation, in particular to electrolyte and a lithium ion battery containing the same.
Background
With the rapid development of society, the increasing demand for sustainable energy is essential to guarantee an ever-increasing world population. The lithium ion battery is an energy storage/conversion system, and can store renewable energy sources such as wind energy, water energy, solar energy and the like, and can store electric energy when a power grid is excessive. The lithium ion battery electrolyte mainly plays a role in conducting lithium ions in the process of battery charge-discharge cycle, and has the function and importance for the lithium battery as blood is in a human body. Therefore, the electrolyte with excellent performance has a critical influence on the performance of the battery. Typical lithium ion electrolyte systems include an electrolyte solvent, a lithium salt and an additive, and when the electrolyte cannot form a stable SEI film on the surface of an electrode, the electrolyte can have a great influence on the cycle life of a battery, so that the generation of the stable SEI film becomes one of the core problems of the improvement of the current lithium battery.
Disclosure of Invention
The invention aims to provide an electrolyte and a lithium ion battery containing the same, which solve the problem that the capacitance of the battery is greatly reduced after the battery is charged and discharged for a certain number of times due to the fact that the stability of a generated SEI film is not high.
The aim of the invention can be achieved by the following technical scheme:
an electrolyte is prepared by adding 8-10% of reinforcing additive into the electrolyte of PC/DEC of 1.0M lithium hexafluorophosphate.
Further, the strengthening additive is prepared by the following steps:
step A1: uniformly mixing pentaerythritol and phosphorus trichloride, introducing nitrogen for protection, reacting for 1-1.5h at the rotation speed of 150-200r/min and the temperature of 85-90 ℃, heating to 140-145 ℃, continuing to react for 7-9h to obtain an intermediate 1, dissolving the intermediate 1 in dioxane, introducing nitrogen for protection, adding methyl vinyl dichlorosilane at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, heating to 85-95 ℃, and reacting for 7-9h to obtain an intermediate 2;
step A2: mixing a modified monomer, 3-mercaptopropyl methyl dimethoxy silane and deionized water, stirring for 10-15min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 4-6h, and regulating the pH value to be neutral to obtain dihydro-terminal polysiloxane;
step A3: dissolving dihydro-terminal polysiloxane in DMF, adding KH570, stirring at 25-30deg.C under 365nm ultraviolet irradiation for 1-1.5 hr, adding intermediate 2 and chloroplatinic acid, heating to 50-60deg.C, and reacting for 10-15 hr to obtain the final product.
Further, the molar ratio of pentaerythritol to phosphorus trichloride in the step A1 is 1:1, and the molar ratio of the intermediate 1 to methyl vinyl dichlorosilane is 2:1.
Further, the dosage ratio of the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 3 mmol/1 mmol/30 mL/2 mmol, and the dosage of the concentrated sulfuric acid is 1-1.5% of the mass sum of the intermediate 3, the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane and the 1, 3-tetramethyl disiloxane.
Further, the molar ratio of mercapto groups on the dihydro-terminated polysiloxane to KH570 in the step A3 is 1:1, the molar ratio of the dihydro-terminated polysiloxane to the intermediate 2 is 1:4, and the concentration of chloroplatinic acid in the mixed solution of the dihydro-terminated polysiloxane and the intermediate 2 is 15-20ppm.
Further, the modified monomer is prepared by the following steps:
step B1: mixing 2,2' -dihydroxybiphenyl and concentrated sulfuric acid, stirring at a rotating speed of 60-120r/min and a temperature of 20-25 ℃, dropwise adding a nitric acid solution, reacting for 3-5h, cooling in an ice water bath, filtering to remove filtrate, obtaining an intermediate 3, uniformly mixing the intermediate 3, acrylonitrile and a benzyl trimethyl ammonium hydroxide methanol solution, and reacting for 8-10h at a rotating speed of 150-200r/min and a temperature of 80-90 ℃ to obtain an intermediate 4;
step B2: uniformly mixing the intermediate 4, methanol and palladium-carbon, introducing nitrogen to replace air, introducing hydrogen to replace air, reacting at 50-55 ℃ and under the pressure of 1MPa until the hydrogen is not absorbed, obtaining the intermediate 5, uniformly mixing 3-glycidoxypropyl methyl diethoxysilane, the intermediate 5 and DMF, and reacting at the rotating speed of 150-200r/min and the pH value of 10-11 for 6-8 hours at the temperature of 60-70 ℃ to obtain the modified monomer.
Further, the ratio of the 2,2' -dihydroxybiphenyl, concentrated sulfuric acid and nitric acid solution in the step B1 is 0.02mol:50mL:15mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 50%, the ratio of the intermediate 3, the acrylonitrile and the benzyl trimethyl ammonium hydroxide in the methanol solution is 40mmol:80mmol:1mL, and the mass fraction of the benzyl trimethyl ammonium hydride in the methanol solution is 40%.
Further, the ratio of the intermediate 4, methanol and palladium carbon in the step B2 is 0.2g:200mL:1g, and the molar ratio of the 3-glycidoxypropyl methyl diethoxysilane to the intermediate 5 is 2:1.
The invention has the beneficial effects that: the electrolyte is prepared by adding a strengthening additive into the electrolyte of PC/DEC (polycarbonate/digital electron-withdrawing) of 1.0M lithium hexafluorophosphate, wherein the strengthening additive is prepared by taking pentaerythritol and phosphorus trichloride as raw materials to react, so that a chlorine atom site on phosphorus trichloride reacts with an alcohol hydroxyl group on pentaerythritol to prepare an intermediate 1, the intermediate 1 reacts with methyl vinyl dichlorosilane, so that a hydroxyl group on the intermediate 1 reacts with a chlorine atom site on the methyl vinyl dichlorosilane to prepare an intermediate 2, a modified monomer and 3-mercaptopropyl methyldimethoxysilane are hydrolyzed and then react with 1, 3-tetramethyl disiloxane to prepare dihydro-terminated polysiloxane, the dihydro-terminated polysiloxane reacts with KH570 under ultraviolet irradiation to prepare a mercapto graft of a double bond on the KH570, then the double bond on the intermediate 2 reacts with Si-H bond on the dihydro-terminated polysiloxane under the action of chloroplatinic acid to prepare an additive, the modified monomer 2' -dihydroxybiphenyl is reacted with a hydroxyl group on the hydroxy-terminated polysiloxane to prepare an amino-3-epoxynitrile, the intermediate 3 is reduced to prepare an amino-5, the intermediate 4-epoxynitrile is prepared by reacting with an intermediate 3, and the intermediate 5-epoxypropyl ether is reduced to prepare an amino-5, the intermediate 5 is reduced to prepare an amino-epoxynitrile, and the intermediate 5 is reduced to prepare an amino-methyl ether, in the hydrolysis polymerization process of 3-mercaptopropyl methyl dimethoxy silane and 1, 3-tetramethyl disiloxane, a reticular molecular chain can be formed, so that the thermodynamic performance of an SEI film is better, solvent molecules are prevented from being directly contacted with an electrode, the co-insertion of the solvent molecules into the electrode is avoided, the cycle performance and the service life of a battery are further improved, the main chain of an additive is enhanced, the effect of overcharge protection can be achieved by containing a biphenyl structure, meanwhile, the chain reaction of hydroxyl free radicals can be prevented by containing an organophosphorus sulfur structure, the safety performance of lithium ions cannot be improved due to the combustion of an organic electrolyte, sulfur has strong electronegativity, the electron absorption capability of the SEI film is stronger, the charge and discharge efficiency of the battery is improved, the side chain contains siloxane structure and trace water in the electrolyte can be hydrolyzed, the adsorptivity with an electrode material is improved, and the stability of the SEI film is improved.
Description of the embodiments
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An electrolyte is prepared by adding 8% of reinforcing additive into the electrolyte of PC/DEC of 1.0M lithium hexafluorophosphate.
The strengthening additive is prepared by the following steps:
step A1: uniformly mixing pentaerythritol and phosphorus trichloride, introducing nitrogen for protection, reacting for 1h at the rotating speed of 150r/min and the temperature of 85 ℃, heating to 140 ℃, continuing to react for 7h to obtain an intermediate 1, dissolving the intermediate 1 in dioxane, introducing nitrogen for protection, adding methyl vinyl dichlorosilane at the rotating speed of 200r/min and the temperature of 60 ℃, heating to 85 ℃, and reacting for 7h to obtain an intermediate 2;
step A2: mixing a modified monomer, 3-mercaptopropyl methyl dimethoxy silane and deionized water, stirring for 10min at the rotation speed of 200r/min and the temperature of 60 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 4h, and regulating the pH value to be neutral to obtain dihydro-terminal polysiloxane;
step A3: dissolving dihydro-terminal polysiloxane in DMF, adding KH570, stirring for 1h under the condition of 60r/min rotation speed, 25 ℃ and 365nm ultraviolet irradiation, adding intermediate 2 and chloroplatinic acid, heating to 50 ℃, and reacting for 10h to obtain the strengthening additive.
The molar ratio of pentaerythritol to phosphorus trichloride in the step A1 is 1:1, and the molar ratio of the intermediate 1 to methyl vinyl dichlorosilane is 2:1.
The dosage ratio of the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 3mmol:1mmol:30mL:2mmol, and the dosage of the concentrated sulfuric acid is 1% of the sum of the mass of the intermediate 3, the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane and the 1, 3-tetramethyl disiloxane.
The molar ratio of mercapto groups to KH570 on the dihydro-terminated polysiloxane in the step A3 is 1:1, the molar ratio of the dihydro-terminated polysiloxane to the intermediate 2 is 1:4, and the concentration of chloroplatinic acid in the mixed solution of the dihydro-terminated polysiloxane and the intermediate 2 is 15ppm.
The modified monomer is prepared by the following steps:
step B1: mixing 2,2' -dihydroxybiphenyl and concentrated sulfuric acid, stirring at a rotating speed of 60r/min and a temperature of 20 ℃, dropwise adding a nitric acid solution, reacting for 3 hours, cooling in an ice water bath, filtering to remove filtrate, preparing an intermediate 3, uniformly mixing the intermediate 3, acrylonitrile and a benzyl trimethyl ammonium hydroxide methanol solution, and reacting at a rotating speed of 150r/min and a temperature of 80 ℃ for 8 hours to prepare an intermediate 4;
step B2: uniformly mixing the intermediate 4, methanol and palladium-carbon, introducing nitrogen to replace air, introducing hydrogen to replace air, reacting at the temperature of 50 ℃ and the pressure of 1MPa until the hydrogen is not absorbed any more to obtain an intermediate 5, uniformly mixing 3-glycidoxypropyl methyl diethoxysilane, the intermediate 5 and DMF, and reacting at the rotating speed of 150r/min and the temperature of 60 ℃ and the pH value of 10 for 6 hours to obtain the modified monomer.
The dosage ratio of the 2,2' -dihydroxybiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step B1 is 0.02mol:50mL:15mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 50%, the dosage ratio of the intermediate 3, the acrylonitrile and the benzyl trimethyl ammonium hydroxide in the methanol solution is 40mmol:80mmol:1mL, and the mass fraction of the benzyl trimethyl ammonium hydride in the methanol solution is 40%.
The dosage ratio of the intermediate 4, methanol and palladium carbon in the step B2 is 0.2g to 200mL to 1g, and the molar ratio of the 3-glycidoxypropyl methyl diethoxysilane to the intermediate 5 is 2:1.
Example 2
An electrolyte is prepared by adding 9% of strengthening additive into the electrolyte of PC/DEC of 1.0M lithium hexafluorophosphate.
The strengthening additive is prepared by the following steps:
step A1: uniformly mixing pentaerythritol and phosphorus trichloride, introducing nitrogen for protection, reacting for 1.3 hours at the rotating speed of 150r/min and the temperature of 88 ℃, heating to 143 ℃, continuing to react for 8 hours to obtain an intermediate 1, dissolving the intermediate 1 in dioxane, introducing nitrogen for protection, adding methyl vinyl dichlorosilane at the rotating speed of 200r/min and the temperature of 65 ℃, heating to 90 ℃, and reacting for 8 hours to obtain an intermediate 2;
step A2: mixing a modified monomer, 3-mercaptopropyl methyl dimethoxy silane and deionized water, stirring for 13min at the rotation speed of 200r/min and the temperature of 65 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 5h, and regulating the pH value to be neutral to obtain dihydro-terminal polysiloxane;
step A3: dissolving dihydro-terminal polysiloxane in DMF, adding KH570, stirring for 1.3h under the condition of rotation speed of 80r/min, temperature of 28 ℃ and ultraviolet irradiation of 365nm, adding intermediate 2 and chloroplatinic acid, heating to 55 ℃, and reacting for 13h to obtain the strengthening additive.
The molar ratio of pentaerythritol to phosphorus trichloride in the step A1 is 1:1, and the molar ratio of the intermediate 1 to methyl vinyl dichlorosilane is 2:1.
The dosage ratio of the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 3mmol:1mmol:30mL:2mmol, and the dosage of the concentrated sulfuric acid is 1.3 percent of the mass sum of the intermediate 3, the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane and the 1, 3-tetramethyl disiloxane.
The molar ratio of mercapto groups to KH570 on the dihydro-terminated polysiloxane in the step A3 is 1:1, the molar ratio of the dihydro-terminated polysiloxane to the intermediate 2 is 1:4, and the concentration of chloroplatinic acid in the mixed solution of the dihydro-terminated polysiloxane and the intermediate 2 is 18ppm.
The modified monomer is prepared by the following steps:
step B1: mixing 2,2' -dihydroxybiphenyl and concentrated sulfuric acid, stirring at a rotating speed of 60r/min and a temperature of 23 ℃, dropwise adding a nitric acid solution, reacting for 4 hours, cooling in an ice water bath, filtering to remove filtrate, preparing an intermediate 3, uniformly mixing the intermediate 3, acrylonitrile and a benzyl trimethyl ammonium hydroxide methanol solution, and reacting for 9 hours at a rotating speed of 150r/min and a temperature of 85 ℃ to prepare an intermediate 4;
step B2: uniformly mixing the intermediate 4, methanol and palladium-carbon, introducing nitrogen to replace air, introducing hydrogen to replace air, reacting at the temperature of 53 ℃ and the pressure of 1MPa until the hydrogen is not absorbed any more to obtain an intermediate 5, uniformly mixing 3-glycidoxypropyl methyl diethoxysilane, the intermediate 5 and DMF, and reacting at the temperature of 65 ℃ and the pH value of 11 for 7h at the rotating speed of 150r/min to obtain the modified monomer.
The dosage ratio of the 2,2' -dihydroxybiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step B1 is 0.02mol:50mL:15mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 50%, the dosage ratio of the intermediate 3, the acrylonitrile and the benzyl trimethyl ammonium hydroxide in the methanol solution is 40mmol:80mmol:1mL, and the mass fraction of the benzyl trimethyl ammonium hydride in the methanol solution is 40%.
The dosage ratio of the intermediate 4, methanol and palladium carbon in the step B2 is 0.2g to 200mL to 1g, and the molar ratio of the 3-glycidoxypropyl methyl diethoxysilane to the intermediate 5 is 2:1.
Example 3
An electrolyte is prepared by adding 10% of reinforcing additive into the electrolyte of PC/DEC of 1.0M lithium hexafluorophosphate.
The strengthening additive is prepared by the following steps:
step A1: uniformly mixing pentaerythritol and phosphorus trichloride, introducing nitrogen for protection, reacting for 1.5 hours at the rotation speed of 200r/min and the temperature of 90 ℃, heating to 145 ℃, continuing to react for 9 hours to obtain an intermediate 1, dissolving the intermediate 1 in dioxane, introducing nitrogen for protection, adding methyl vinyl dichlorosilane at the rotation speed of 300r/min and the temperature of 70 ℃, heating to 95 ℃, and reacting for 9 hours to obtain an intermediate 2;
step A2: mixing a modified monomer, 3-mercaptopropyl methyl dimethoxy silane and deionized water, stirring for 15min at the rotation speed of 300r/min and the temperature of 70 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 6h, and regulating the pH value to be neutral to obtain dihydro-terminal polysiloxane;
step A3: dissolving dihydro-terminal polysiloxane in DMF, adding KH570, stirring for 1.5h under the condition of rotating speed of 80r/min, temperature of 30 ℃ and 365nm ultraviolet irradiation, adding intermediate 2 and chloroplatinic acid, heating to 60 ℃, and reacting for 15h to obtain the strengthening additive.
The molar ratio of pentaerythritol to phosphorus trichloride in the step A1 is 1:1, and the molar ratio of the intermediate 1 to methyl vinyl dichlorosilane is 2:1.
The dosage ratio of the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 3mmol:1mmol:30mL:2mmol, and the dosage of the concentrated sulfuric acid is 1.5% of the sum of the mass of the intermediate 3, the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane and the 1, 3-tetramethyl disiloxane.
The molar ratio of mercapto groups to KH570 on the dihydro-terminated polysiloxane in the step A3 is 1:1, the molar ratio of the dihydro-terminated polysiloxane to the intermediate 2 is 1:4, and the concentration of chloroplatinic acid in the mixed solution of the dihydro-terminated polysiloxane and the intermediate 2 is 20ppm.
The modified monomer is prepared by the following steps:
step B1: mixing 2,2' -dihydroxybiphenyl and concentrated sulfuric acid, stirring at a rotating speed of 120r/min and a temperature of 25 ℃, dropwise adding a nitric acid solution, reacting for 5 hours, cooling in an ice water bath, filtering to remove filtrate, obtaining an intermediate 3, uniformly mixing the intermediate 3, acrylonitrile and a benzyl trimethyl ammonium hydroxide methanol solution, and reacting for 10 hours at a rotating speed of 200r/min and a temperature of 90 ℃ to obtain an intermediate 4;
step B2: uniformly mixing the intermediate 4, methanol and palladium-carbon, introducing nitrogen to replace air, introducing hydrogen to replace air, reacting at the temperature of 55 ℃ and the pressure of 1MPa until the hydrogen is not absorbed any more to obtain an intermediate 5, uniformly mixing 3-glycidoxypropyl methyl diethoxysilane, the intermediate 5 and DMF, and reacting at the temperature of 70 ℃ and the pH value of 11 for 8 hours at the rotating speed of 200r/min to obtain the modified monomer.
The dosage ratio of the 2,2' -dihydroxybiphenyl, the concentrated sulfuric acid and the nitric acid solution in the step B1 is 0.02mol:50mL:15mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the nitric acid solution is 50%, the dosage ratio of the intermediate 3, the acrylonitrile and the benzyl trimethyl ammonium hydroxide in the methanol solution is 40mmol:80mmol:1mL, and the mass fraction of the benzyl trimethyl ammonium hydride in the methanol solution is 40%.
The dosage ratio of the intermediate 4, methanol and palladium carbon in the step B2 is 0.2g to 200mL to 1g, and the molar ratio of the 3-glycidoxypropyl methyl diethoxysilane to the intermediate 5 is 2:1.
Comparative example 1
This comparative example was identical to example 1 except that no modifying monomer was added.
Comparative example 2
This comparative example was prepared by adding 3-mercaptopropyl methyldimethoxysilane as compared with example 1, and the remaining steps were the same.
And (2) dissolving polyvinylidene fluoride in M-methylpyrrolidone, wherein the mass fraction of the polyvinylidene fluoride is 5%, adding lithium cobaltate and acetylene black, uniformly mixing, uniformly loading the circular aluminum collector sheet with a scraper coating method, drying to obtain a positive electrode sheet, wherein the positive electrode sheet is a working electrode, the lithium metal is a counter electrode, a Celgard2400 polypropylene porous membrane is a diaphragm, the electrolyte prepared in examples 1-3 and comparative examples 1-2 is assembled into a battery in a glove box filled with argon, detecting capacitance at current intensity of 0.2C, voltage of 4.2V and cycle number of 20 weeks, 40 weeks, 60 weeks, 80 weeks and 100 weeks, and the detection results are shown in table 1.
TABLE 1
From the above table, the present application is able to maintain capacitance after multiple cycles.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (4)

1. An electrolyte, characterized in that: is prepared by adding 8-10% of strengthening additive into the electrolyte of PC/DEC of 1.0M lithium hexafluorophosphate;
the strengthening additive is prepared by the following steps:
step A1: uniformly mixing pentaerythritol and phosphorus trichloride, introducing nitrogen for protection, reacting for 1-1.5h at the rotation speed of 150-200r/min and the temperature of 85-90 ℃, heating to 140-145 ℃, continuing to react for 7-9h to obtain an intermediate 1, dissolving the intermediate 1 in dioxane, introducing nitrogen for protection, adding methyl vinyl dichlorosilane at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, heating to 85-95 ℃, and reacting for 7-9h to obtain an intermediate 2;
step A2: mixing a modified monomer, 3-mercaptopropyl methyl dimethoxy silane and deionized water, stirring for 10-15min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 4-6h, and regulating the pH value to be neutral to obtain dihydro-terminal polysiloxane;
step A3: dissolving dihydro-terminal polysiloxane in DMF, adding KH570, stirring for 1-1.5h under the condition of 25-30deg.C and 365nm ultraviolet irradiation at rotation speed of 60-80r/min, adding intermediate 2 and chloroplatinic acid, heating to 50-60deg.C, and reacting for 10-15h to obtain reinforced additive;
the molar ratio of the pentaerythritol to the phosphorus trichloride in the step A1 is 1:1, and the molar ratio of the intermediate 1 to the methyl vinyl dichlorosilane is 2:1;
the dosage ratio of the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 3 mmol/1 mmol/30 mL/2 mmol;
the molar ratio of mercapto groups to KH570 on the dihydro-terminal polysiloxane in the step A3 is 1:1, and the molar ratio of the dihydro-terminal polysiloxane to the intermediate 2 is 1:4;
the modified monomer is prepared by the following steps:
step B1: mixing 2,2' -dihydroxybiphenyl and concentrated sulfuric acid, stirring at a rotating speed of 60-120r/min and a temperature of 20-25 ℃, dropwise adding a nitric acid solution, reacting for 3-5h, cooling in an ice water bath, filtering to remove filtrate, obtaining an intermediate 3, uniformly mixing the intermediate 3, acrylonitrile and a benzyl trimethyl ammonium hydroxide methanol solution, and reacting for 8-10h at a rotating speed of 150-200r/min and a temperature of 80-90 ℃ to obtain an intermediate 4;
step B2: uniformly mixing the intermediate 4, methanol and palladium-carbon, introducing nitrogen to replace air, introducing hydrogen to replace air, reacting at 50-55 ℃ and under the pressure of 1MPa until the hydrogen is not absorbed any more to obtain an intermediate 5, uniformly mixing 3-glycidoxypropyl methyl diethoxysilane, the intermediate 5 and DMF, and reacting at the rotating speed of 150-200r/min and the temperature of 60-70 ℃ and the pH value of 10-11 for 6-8 hours to obtain a modified monomer;
the dosage ratio of the 2,2' -dihydroxybiphenyl, concentrated sulfuric acid and nitric acid solution in the step B1 is 0.02mol:50mL:15mL, and the dosage ratio of the intermediate 3, the acrylonitrile and the benzyl trimethyl ammonium hydroxide in methanol solution is 40mmol:80mmol:1mL;
the dosage ratio of the intermediate 4, methanol and palladium carbon in the step B2 is 0.2g to 200mL to 1g, and the molar ratio of the 3-glycidoxypropyl methyl diethoxysilane to the intermediate 5 is 2:1.
2. An electrolyte according to claim 1, wherein: the dosage of the concentrated sulfuric acid in the step A2 is 1 to 1.5 percent of the mass sum of the modified monomer, the 3-mercaptopropyl methyl dimethoxy silane and the 1, 3-tetramethyl disiloxane.
3. An electrolyte according to claim 1, wherein: the concentration of chloroplatinic acid in the mixed solution of the dihydro-terminal polysiloxane and the intermediate 2 in the step A3 is 15-20ppm.
4. A lithium ion battery, characterized in that: the lithium ion battery comprising the electrolyte of any one of claims 1-3.
CN202311371375.4A 2023-10-23 2023-10-23 Electrolyte and lithium ion battery containing same Active CN117117328B (en)

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